Poly(propylene carbonate) (hereinafter also referred to as “PPC”) is a polymer known since the late 1960's when it was first synthesized by Inoue and co-workers. Until recently, high molecular weight PPC has been predominantly synthesized using zinc carboxylate catalysts to copolymerize propylene oxide and CO2. The resulting material was the focus of intense investigation and several companies have explored applications for the material as a commodity thermoplastic. To date, PPC has been commercialized only as a sacrificial polymer in applications where the clean thermal decomposition of PPC is advantageous. Commercialization of the material for thermoplastic applications has been complicated by poor thermal and processing properties. Recently, transition metal complexes have been developed for the copolymerization of CO2 and epoxides, but such complexes have not been fully exploited and/or optimized in the preparation of improved PPC materials.